Physicochem. Probl. Miner. Process.

, 57(3), 2021, 97-111 Physicochemical Problems of Mineral Processing

ISSN 1643-1049
http://www.journalssystem.com/ppmp
© Wroclaw University of Science and Technology

Received December 30, 2020; reviewed; accepted April 13, 2021

A study on the dissolution kinetics of iron oxide leaching from clays

by oxalic acid
Volkan Arslan
General Directorate of Minerals Research and Exploration, 42100, Konya, Turkey.

Corresponding author: volkanarslan76@hotmail.com

Abstract: Clay is widely used in a number of industries due to its special properties like fine particle
size, brightness and whiteness, chemical inertness, platy structure, etc. In this study, the general
characteristics of clays have been investigated by XRF, XRD, FT-IR, TG-DTA and SEM. The presence of
iron as an impurity decreases its commercial value due to giving unwanted colors to clay mineral.
Therefore, the dissolution capacity of clay ore was investigated by oxalic acid leaching. Under optimized
leaching conditions (0.8 M oxalic acid concentration, 85°C reaction temperature, 1.75 ambient pH, -
106+75 µm particle size, 15% w/v solids concentration and 150 min. leaching time) with 250 rpm
stirring, 83.90% of Fe2O3 was removed. The amount of iron oxide, the main impurity in the clay, has
been reduced from 2.70 to 0.40%. The iron dissolution kinetics was mainly controlled by internal
diffusion control of shrinking core model and activation energy, Ea, of 26.29 kJ/mol was obtained for
the process. The results also showed that the studied clays have adequate characteristics for ceramics
industry, earthenware and porcelain production.

Keywords: clay, physico-chemical characterization, chemical leaching, oxalic acid, dissolution kinetic,
activation energy

1. Introduction
Clay is a term used to describe either the size of the individual particles present in a deposit (clay size
fraction) or specific minerals (clay minerals) of small size typically less than 0.002 mm in dimension.
This mineral mostly contains impurities such as limestone, silica, mica, and iron oxide and has a
yellowish, reddish, or brown color (Fabio et al., 2009; Vitra, 2009; Nzeukou et al., 2013; Abuh et al.,
2014; Njoka et al., 2015). The chemical and physical properties of clay minerals are of great importance
to industry, agriculture and the environment owing to their abundance, high specific surface area, high
layer charge, laminar morphology and chemical reactivity with both neutral and charge species
(Murray, 1999; Hoidy et al., 2009). Clays are used as raw materials in many industrial fields such as
ceramics, paper, paint, petroleum industry, clarification of various effluents, catalysis, pharmaceu-
tical, cosmetics and tooth paste industries. The common impurities of the natural mineral are iron
oxides and quartz, which impart poor quality to the finished products and cause other problems, if
present in excess. For the production of high-quality materials, the iron content in clay should be
lower than 0.8% (Celik, 2010). Many methods, such as flotation, gravity separation, chemical leaching,
reductive roasting and magnetic separation are used for the beneficiation of clay (Chang, 2002; Abel,
2012; Fadil-Djenaboua, 2015; Milosevic, 2017).
Chemical leaching is a method that aims to remove unwanted contaminants from minerals using
organic and inorganic acids. Among the inorganic acids, the most widely used are hydrofluoric,
hydrochloric, sulfuric and perchloric acids. Especially HF, are very dangerous to human health and the
environment, and must be recycled. On the other hand, the clay products must be required washing
after the leaching, since hydrochloric and sulfuric acids can easily contaminate the product with SO42-
and Cl- (Santos et al., 2015; Tuncuk and Akcil, 2016). Organic acids (oxalic, citric, ascorbic, gluconic,

DOI: 10.37190/ppmp/135749
98 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

malic acid) are often preferred because of their advantages such as higher iron removal yield, ability to
proceed in a wide pH ranges as they prevent iron precipitation and being a more eco-friendly product
compared to inorganic acids (Panias et al., 1996; Mandal and Banerjee, 2004; Lee et al., 2006; Lori et al.,
2007; Zhong et al., 2013; Tuncuk and Akcil, 2016; Lima et al., 2017; Vapur et al., 2017; Garg and Skibsted,
2019; Pariyan et al., 2019). Especially, oxalic acid has been reported to be more effective for iron removal
and brightness improvement (Ambikadevi and Lalithambika, 2000).
Leaching kinetics is important in dissolving metals and metal compounds and in designing the
leaching process. To optimize the leaching efficiency, the dissolution kinetics should be very well
analyzed. The major models that have been developed for non-catalytic fluid-solid reactions are the
shrinking core, shrinking particle, homogeneous, grain, uniform pore and random pore models (Gbor
and Jia, 2004; Ghassa et al., 2017). Among these models, the shrinking core model has been widely used
in the area of hydrometallurgy to model leaching systems. A model is determined according to the
results of the leaching experiments and the data obtained from the model are used to determine the
activation energy (Cornell and Schwertmann, 2003; Bonneville et al., 2009; Hursit et al., 2009; Shi et al.,
2011; Sultana et al., 2014; Ghasemi and Azizi, 2017; Lima et al., 2017; Zhang et al., 2017; Li et al., 2019;
Yang and Li, 2020).
In this study, X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), scanning electron
microscope (SEM), thermo gravimetric- differential thermal analysis (TG-DTA) and fourier
transformed infrared spectroscopy analysis (FT-IR) were performed to determine the characteristic
properties of clay. After that, organic acids such as citric, oxalic, malic, gluconic, malonic acid were used
to select the most suitable acid for this study in the first stage chemical leaching experiments and the
most suitable organic acid was determined. In the second stage leaching experiments, the clay sample
was subjected to chemical leaching with oxalic acid (C2H2O4) to make it suitable for various industries
such as filling, coating, ceramic, paint, cement etc. In the research on dissolution kinetics, dissolution
curves were drawn, activation energy was calculated and it was investigated whether it was suitable
for chemical leaching reaction using oxalic acid.

2. Materials and methods

2.1. Material
Iron-containing clay from Doganhisar region in Turkey was selected for experimental studies. The
study covered over approximately 25 km2 including Ayaslar and Doganhisar formations. The clay
sample was passed through a 500 µm diameter sieve before use. The sample was used as such without
any further modification for the acid leaching treatments.

2.2. Characterization techniques

The clay sample was characterized by XRF, XRD, FT-IR, TG-DTA and SEM. All characterization
analyzes were performed in General Directorate of Mineral Research and Exploration Analysis
Laboratory and Hitit University Scientific Research Center. The chemical composition was determined
by X-ray fluorescence spectroscopy (PW2400, Phillips) with X-ray tube of rhodium anode and
scintillation detector with a current 40 mA and voltage 40 mV. Bulk clay samples crushed to fine
powder were mixed lithium tetra borate for chemical analysis. The ignition loss was measured by
calcination at 1000°C. The X-ray diffraction data was collected using a Philips analytical X-ray
instrument, X’Pert-MPD (PW 3020 vertical goniometer and PW 3710 MPD control unit) employing
Bragg-Brentano para focusing optics. The XRD patterns were recorded in the range of 10-70° with a
scanning rate of 2°/min. Morphology of the clay samples was determined by SEM. The samples were
deposited on a sample holder with an adhesive carbon foil and sputtered with gold. The clay samples
were studied with a Philips 30 Analytical Scanning Electron Microscope. Particle images were obtained
with a secondary electron detector. Simultaneous thermal analysis (Netzsch STA 409) under air
atmosphere was used for differential thermal analysis and thermo-gravimetric analysis (DTA/TGA).
The temperature was increased from room temperature to 1200°C at a rate of 10°C/min, kept at this
maximum temperature for 10 min. FT-IR spectra were recorded on a Perkin-Elmer infrared
99 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

spectrophotometer as KBr pellets with resolution of 4 cm-1, in the range of 450-4000 cm-1. The sample
and analytical grade KBr were dried at 100°C over-night prior to the FT-IR analysis.

2.3. Chemical leaching experiments

In the first stage chemical leaching experiments, the efficiency of various organic acids was investigated.
For all experiments very pure (>99%) citric (Merk), oxalic (Merk), malic (Merk), gluconic (Merk) and
malonic (Merk) acids were used as reducing agents. Chemical leaching experiments performed to
determine the most suitable organic acid in 500 ml flasks, 400 ml acid solution, 250 rpm stirring speed,
0.5 M acid concentration, 60°C leaching temperature, 2.00 ambient pH, -106+75 µm particle size, 15%
solid concentration and 120 minutes leaching time. In the first stage experiments, the most effective
organic acid was determined and the effect of this acid on Fe2O3 and TiO2 removal from the clay was
investigated under varied leaching conditions.
In the second stage chemical leaching experiments, the leaching tests were carried out in a round
bottomed flask (500 ml) which was kept stirred in a heating mantle, for each run, 400 ml of oxalic acid
solution (C2H2O4, reagent grade) at different concentrations were added to the flask and the temperature
was set to the desired value. Then, 40.0 g of clay was added to the flask while 250 rpm magnetic stirring.
Periodically, a 10 ml sample was taken from the leach slurry and was centrifuged immediately at 250
rpm during 20 min. A clear 5 ml aliquot of the solution was collected for total iron determination. All
leaching tests were made at atmospheric pressure. A watch glass was fitted to the flask to prevent
evaporation. Subsequently, the slurry was filtered, and the residue was washed with hot distilled water,
dried, and analyzed for iron using atomic absorption spectrophotometer (AAS). Experiments were done
in triplicate. The variables studied were oxalic acid concentrations (0.01, 0.05, 0.10, 0.30, 0.50, 0.80 and
1.0 M), reaction temperature (15, 30, 45, 60, 75, 85 and 100°C), pH (1.25, 1.50, 1.75, 2.00, 2.25, 2.50 and
3.00), particle size (-500+250, -250+150, -150+106, -106+75 and -75+38 µm), solids concentration (5, 10,
15, 20, 25, 30 and 40 w/v) and leaching time (30, 60, 90, 120, 150, 180 and 210 min). The clay leaching
process was simulated using the SuperPro Designer Program and the flow sheet of the experimental
steps was given in Fig. 1.

Fig. 1. Clay product flow sheet created with SuperPro Designer Software

2.4. Kinetic study of leaching process

In a heterogeneous solid/liquid leaching reaction system, the soluble reactants diffuse across the
interface and/or through the solid layer first (Zhang et al., 2016; Li et al., 2017; Tao et al., 2021). The
shrinking core model assumes that the solid particles used in the experiments gradually shrink during
the leaching process, leading to the formation of a porous layer on the surface of the unreacted core.
The shrinking core model is one of the most important and widely used kinetic models in leaching of
100 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

clay minerals. Experimental data graphic is plotted against time of each model equation to determine
the controlling step. The model with the closest correlation coefficient to one is thought to best control
the leaching process (Dehgan et al., 2009; Sultana and Kurny, 2012; Legorreta et al., 2015; MacCarthy et
al., 2016; Tanda et al., 2018; Pariyan et al., 2019; Cetintas and Bingol, 2020).
If the reaction rate is controlled by a surface chemical reaction, the integrated rate equation of the
shrinking core model can be described as follows:
1 − (1 − α)&/( = k , t (1)
If the reaction rate is controlled by diffusion through the product layer, the integrated rate equation
of the shrinking core model can be described as follows:
1 − 2⁄3𝛼 − (1 − α)2/( = k 3 t (2)
where α is the fraction of the clay ore reacted, t is the leaching time (min), kr is the apparent rate constant
for the surface chemical reaction, kd is the apparent rate constant for the diffusion through the product
layer (Antonijevic et al., 2004; Baba and Adekola, 2012; Baba et al., 2014; Baba et al., 2015; Zhang et al.,
2019).
The Arrhenius equation is a formula for the temperature dependence of reaction rate. This equation
has a vast and important application in determining rate of chemical reactions, and for calculation of
activation energy, as well. The activation energy for mentioned reactions could be calculated by
Arrhenius equation (Eq. 3):
78 &
ln(k) = ln(A) − 9
.; (3)
where, A is a pre-exponential factor (mol/cm2·s), Ea is the apparent activation energy (kJ/mol), and
R is the molar gas constant (kJ/mol·K) (Ayanda and Adekola, 2012; Du et al., 2016; Sanda and Taiwo,
2016; Naviaux et al., 2019).

3. Results and discussion

3.1. Chemical and mineralogical compositions
From the phase (mineralogical) analysis and XRD report it could be concluded that the major
component of the clay is mica and illite, followed by quartz, calcite, feldspar and trace amounts of
chlorite in decreasing order of abundance (Fig. 2). The chemical composition of the sample was given
in Table 1. Size distribution of the sample was as follows: -500+250 µm: 14.27%, -250+150 µm: 20.13%, -
150+106 µm: 30.32%, -106+75 µm: 31.83%, -75+38 µm: 3.45%.

Fig. 2. X-ray diffraction patterns for a Doganhisar clay sample

Table 1. The chemical composition of the clay sample

Composition SiO2 Al2O3 Fe2O3 MgO CaO P2O5 K2O TiO2 LOI Whiteness
Content (wt, %) 62.40 20.63 2.70 0.60 0.25 0.30 2.56 1.04 7.21 61.06
101 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

3.2. Thermal analysis (DTA/TGA)

In general, clay materials contain three kinds of water molecules in their structure. First layer, the
physisorbed and interlayer water are loosely bound and are mobile that they can be removed by
heat treatment below 200°C. The water molecules present in the first coordination sphere of the
interlayer ions is strongly bonded and require higher temperature in the range of 250-450°C for their
removal. Finally, the structural hydroxyl groups can condense and dehydrate in the temperature range
of 450-750°C. DTA can be applied to identify and to estimate various types of clay minerals. These
minerals can be differentiated by determining the temperature at which the endothermic and
exothermic peaks occur. From the TG analysis, it was found that the clay sample lost all its moisture
till 100-150°C. Since the total weight loss in the clay mineral is not much at high temperatures, this
indicates that it can be used at high temperature applications. Besides, DTA curve gave an exothermic
peak at 450-470°C and this endothermic peak supported that thermal degradation took place between
450 and 700°C. The reaction decomposition started at 610°C, made an endothermic peak at about
730°C, and was complete at 925°C (Fig. 3). In the review of the literature, it was determined that the
clay in this region shows similar properties (Rahman and Muneer, 2005; Wu et al., 2011; Sandler,
2013; Celik et al., 2013; Erdogan, 2015). As a complementary remark regarding the thermal analysis, it
should be mentioned that the common characteristics for all clays are the presence of two ranges of
endothermic peaks, which are related to the decomposition of Al and Fe hydroxides and the
dehydroxylation of the clay mineral.

Fig. 3. TG-DTA curves of Doganhisar clay (heating rate: 10°C/min)

3.3. Fourier transformed infrared (FT-IR) analysis

Fig. 4 shows the FT-IR spectra of the clay sample. They range from 550 to 3000 cm-1. The peaks at
position 570.05, 695.78, 751.15, 801.43, 911.68 and 1000.94 cm-1 lies within the mid infrared region
(550-1000 cm-1). The spectrum of the original clay suggests that it contains poorly crystallized
components, evidenced by the absorption band at 1000 cm-1 and inflexion at 1220 cm-1 due to
amorphous silica. The raw clay spectrum also contains a broad band at 1450 cm-1, due to the calcite
impurity. The IR spectra also suggest that the Al3+, Fe3+ and Mg2+ ions occupy octahedral sites, since
the hydroxyl bending peaks of Al2OH, AlFeOH and AlMgOH vibrations are present at 911.68 and
801.43 cm-1 respectively. An O-H stretching band located around 2351 cm-1 has been reported in Mg
and Al-enriched dioctahedral mica (Madejova et al., 1998; Gates et al., 2002; Temuujin et al., 2002;
Temuujin et al., 2004; Njoka et al., 2015).

3.4. Scanning electron microscopy (SEM)

Representative scanning electron micrographs of the clay sample is presented in Fig. 5 which shows
the morphological features. On further examination of SEM micrographs, the larger clay mineral
102 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

particles seems to consist of much smaller platelets which indicates that the clay sample is made up
of very fine particles. It shows a sample composed entirely of well-rounded quartz with small oval
depression fringed by clay. The presence of iron oxide has been shown by appearance of very bright
sections and this confirms the results of XRD and FT-IR.

Fig. 4. FT-IR spectrum of clay sample from Doganhisar formation

Fig. 5. SEM photomicrographs of clay sample from Doganhisar formation

3.5. Chemical leaching results

3.5.1. Determination of the optimized organic acid
The effects of different organic acids on the ability to dissolve Fe2O3 and TiO2 in clay are shown in Table
2. Oxalic acid has been found to be the most effective leachant. Also, the order of activity of organic
acids is as follows: oxalic>citric>malonic>gluconic>malic acid. Achieving the best results with oxalic
acid can be explained by its acidity, reducing capacity, and complexing effect (Ambikadevi and
Lalithambika, 2000; Saikia et al., 2003).

3.5.1. Oxalic acid leaching results

3.5.1.1. Effect of pH on the iron dissolution efficiency
In this experiment, the effect of pH on iron dissolution efficiency was investigated. Chemical leaching
experiments with pH varied from 1.00 to 3.00 were carried out versus time at 50°C, at 0.3 M oxalic acid
concentration, -150 + 106 µm particle size and 20% solids rate. It was observed that above pH 2.0, the
103 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

amount of dissolved iron in the filtered solution rapidly decreased. This is probably because iron starts
to precipitate when pH is greater than 2 (Fig. 6). Investigating the effect of pH, very high iron dissolution
efficiency could not be obtained and the best dissolution efficiency was found as 28.75% at pH 1.75.

Table 2. Fe2O3 content in the clay after chemical leaching with different organic acids

Organic acids Fe2O3 content (%) TiO2 content (%)

Raw material 2.70 1.04
Citric acid 0.93 0.71
Gluconic acid 1.51 0.81
Malic acid 1.78 0.89
Malonic acid 1.23 0.76
Oxalic acid 0.71 0.64

Fig. 6. Effect of pH on iron removal from clay

3.5.1.2. Effect of particle size

The experiments were carried out at pH 1.75, at 50°C, at 0.3 M acid concentration and 20% solids rate.
The results of this investigation are summarized in Fig. 7. When Fig. 7 was investigated, it was clearly
seen that the dissolution efficiency of the clay ore decreases as the particle size increases. Apparently,
the greater the particle size, the lesser the fraction, that is being dissolved owing to the increasing surface
area, exhibited by small powdered particle size (Baba et al., 2009). As a result, it was determined that
the best iron dissolution efficiency was realized at -106+75 µm particle size in this experiment. In this
particle size, iron dissolution efficiency was 36.87%.

3.5.1.3. Effect of solid density

This experiment was carried out by varying the solids ratio from 5 to 40% (w/v) under the optimized
conditions of the previous experiment. It was determined that as the solids rate increased, the iron
dissolution efficiency increased and then declining slowly after reaching a maximum of 15% (Fig. 8). At
higher concentrations (>15%, w/v), the suspension probably becomes sufficiently thick restricting free
mixing of clay particles with the leaching solution that results in decrease of the rate (Mandal and
Banerjee, 2004). Finally, the optimized solids rate (15% w/v) iron dissolution efficiency was determined
as 57.60%.

3.5.1.4. Effect of oxalic acid concentration

The dissolution of iron oxides versus time at 50°C, using various concentrations of oxalic acid (0.01,
0.05, 0.10, 0.30, 0.50, 0.80 and 1.0 M), is shown in Fig. 9. The results depicted in Fig. 9 show that the
104 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

Fig. 7. Effect of particle size on iron removal from clay

Fig. 8. Effect of solid density on iron removal from clay

yield of the reacted ore increases linearly with increasing acid concentration in the range 0 to 210
min. An increase in the amount of the ore reacted with leaching time were observed within the acid
concentration ranges (0.01-0.8 M), where the dissolution increased from 9.50 to 72.60% at 150 min,
respectively. However, further increase of the acid to 1.0 M, reduces the amount of the ore reacted to
69.11% at 150 min contact. The possible reason for this observation could be attributed to a
precipitation phenomenon (Baba and Adekola, 2012; Baba et al., 2015). Hence, 0.8 M oxalic acid
concentration with high value of dissolution was selected for further investigations in this study.

3.5.1.5. Effect of leaching temperature

Oxalic acid concentration was kept constant at 0.8 M and yield of iron dissolution at various
temperatures (15, 30, 45, 60, 75, 85 and 100°C) was given in Fig. 10. It was seen that the iron dissolution
yield was better especially at temperatures above 75°C. The dissolution curves appear to be parabolic
as temperature increases from 45 to 100°C. That is, the dissolution of iron with oxalic acid has to be
thermally activated to be efficient. This, on the other hand, is an indicator that the system exhibits a
chemical control. The possible reason, as earlier observed, could be due to the retardation of the
rate of clay oxidation at elevated temperatures. Hence, the higher the temperature, the higher is the
percentage of iron impurities removal (Antonijevic et al., 2004; Hernandez et al., 2013; Saklar and
Yorukoglu, 2015). At 85°C, for example, the dissolution reached 83.90% within 150 min.
105 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

Fig. 9. Effect of oxalic acid concentrations on iron removal from clay

Fig. 10. Effect of leaching temperatures on iron removal from clay

3.6. Dissolution Kinetics Analysis

The results obtained during kinetics study of iron extraction, evaluating the effect of oxalic acid
concentration and temperature in the range 298 to 373 K were treated with the decreasing core model
for heterogeneous reactions both for diffusive and chemical control. The shrinking core models, which
have been tried by several researchers, were tested to explain the dissolution kinetics of the leaching
process.
The dissolution data in Figs. 9 and 10 were calculated according to the shrinking core model of Eqs.
1 and 2. It was important to note that the dissolution data fitted perfectly with the model Eq. 1, where
an average correlation, R2 value was obtained. From the leaching time versus 1 − (1 − α)&/( plots in Fig.
11, the regression coefficient (R2) values for the oxalic acid concentrations of 0.01 M, 0.05 M, 0.1 M, 0.3
M, 0.5 M, 0.8 M and 1.0 M were determined as 0.97, 0.98, 0.97, 0.98, 0.93, 0.92 and 0.93, respectively.
High R2 values indicated that the dissolution of iron from the clay mineral was controlled by diffusion.
The dissolution data in Fig. 9 were linearized with the model Eq. 1 as seen in Fig. 11.
From Fig. 11, the slope of each lines was calculated and recorded as apparent rate constants, k, from
which the plot of lnk, versus ln[C2H2O4] was obtained (Fig. 12) for the evaluation of reaction order for
the process. The plots, shown in Fig. 13, were obtained through Eq. 1 using the dissolution data in Fig.
10. From the graphs drawn for 15, 30, 45, 60, 75, 85 and 100°C temperature values, 0.97, 0.96, 0.97, 0.96,
0.93, 0.89 and 0.89 regression coefficients (R2) were obtained, respectively. These results indicate that
106 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

Fig. 11. Plot of 1-(1-α)1/3 against leaching time at different [C2H2O4]

Fig. 12. Plot of lnk vs. ln[C2H2O4]

iron dissolution from the clay mineral occurs by diffusion through an inert product layer. The Arrhenius
plot considering the apparent rate constants, kr, was obtained by applying Eq. 1 to leaching
experimental data (Fig. 14). From the slope of Fig. 14, using Eq. 3, the activation energy (Ea) for the
dissolution of clay in C2H2O4 is 26.29 kJ mol-1. This value clearly suggests that the reaction for this
process is diffusion controlled as proposed by several investigators (Ajemba and Onukwuli, 2012;
Sultana et al., 2014; Legorreta et al., 2015; Gao et al., 2019; Pariyan et al., 2019; Yang and Li, 2020). So, it
is reasonable that the iron removal is higher at the elevated temperatures.

3.7. Technological Properties

While the whiteness degree of the untreated clay was 61.06%, the whiteness degree of the clay sample
was determined as 90.60% after oxalic acid leaching. This value is much higher than 80% as specified
for filling, coating and ceramic grade clay. Usage standard values of raw material and leached clay for
filling, coating, ceramic, paint and cement industries were given in Table 3 (TS 5396). It was clearly seen
that the raw material, especially because of the Fe2O3 and TiO2 values were above the desired standards,
was not suitable for ceramic or other purposes. The clay sample obtained after oxalic acid leaching meets
all the requirements in order to be used as a raw material or filler material in the all industries except
paint industry. Further study on removal of iron from clay is necessary to obtain higher quality clay
from the Doganhisar region.
107 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

Fig. 13. Plot of 1-(1-α)1/3 vs. leaching time at different temperatures

Fig. 14. Arrhenius relation lnk vs. 1/T (1/K)

Table 3. Technical properties of raw material and leached clay and standard values of clay for various industries

Leached
Characteristics Fillinga Coveringa Ceramica Painta Cementa Raw material
clay
Al2O3 (min) 20 30 28 39 20 20.63 32.15
SiO2 (min) 45 45 59 45 51 62.40 65.60
CaO (max) 1.0 1.0 0.1 0.02 0.1 0.25 0.08
TiO2 (max) 0.5 0.5 0.4 0.6 0.5 1.04 0.37
Fe2O3 (max) 0.5 0.5 0.5 0.9 0.4 2.70 0.40
K2O (max) - - 0.3 0.2 0.5 2.56 0.25
pH of the
4.5-7.5 4.5-7.5 4.5-7.5 4.5-7.5 4.5-7.5 - 5.0-5.5
extract
Whiteness
80 80 80 - - 61.06 90.60
(min)
LOI (max) 14.0 15.5 14.0 15.5 14.0 7.21 13.79
a Turkish Standards Institution TS 5396, 1987
108 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

Conclusions
Based on the results obtained in this study, the following conclusions can be drawn:
The Doganhisar clay was characterized by chemical, mineralogical and thermal analysis. All applied
methods were in a good agreement. The studied clays have a major content of mica and illite minerals
with medium amount of quartz, calcite and feldspar, followed by and trace amounts of chlorite in
decreasing order of abundance.
In SEM examinations, it was seen that clay samples are mica minerals. It shows a sample composed
entirely of well-rounded quartz with small oval depression fringed by clay. The presence of iron oxide
has been shown by appearance of very bright sections.
From the TG analysis, it was found that the clay sample lost all its moisture till 100-150°C. Besides,
DTA curve gave an exothermic peak at 450-470°C and this exothermic peak supported that thermal
degradation took place between 450 and 700°C. Sintering started at around 400°C and was completed
at 700°C.
Chemical methods (specially leaching with organic acids) are effective and useful in dissolving
iron impurities from clays. Among these organic acids (oxalic, gluconic, citric, malic, malonic, ascorbic
acids, etc.), especially oxalic acid is much more effective than others in removing iron in the clay. In
chemical leaching experiments, acid concentration, reaction temperature, pH, particle size, solids
concentration and leaching time were investigated. The optimized chemical leaching conditions were
determined as 1.75 pH, -106+75 µm particle size, 15% w/v solids concentration, 0.8 M oxalic acid
concentration, 85°C temperature and 150 min. leaching time. As a result, the amounts of iron oxide and
titanium oxide, the main impurities in the clay, were reduced from 2.70% to 0.40% and from 1.04% to
0.37%, respectively in the optimized leaching conditions.
In the research on dissolution kinetics, dissolution curves were analyzed and determined to be
suitable for chemical reaction. As a result of the calculations, the activation energy was determined as
26.29 kJ mol-1. Consequently, Doganhisar clay has qualities necessary for the manufacture of stoneware
and porcelain industry, and it is an alternative raw material for the filling, covering, ceramic and cement
industries.

Acknowledgments
I am grateful to Tokluoglu Mining Company for the supply of clay samples, General Directorate of
Mineral Research and Exploration Analysis Laboratory and Hitit University Scientific Technical
Application and Research Center for all analyses.

References
ABEL, O.T., OLADIMEJI, L.A., OLUWATOYIN, O.A., 2012. Compositional Features and Industrial Application of
Ikere Kaolinite Southwestern Nigeria. Res. J. Engineer. Appl. Sci. 1, 5, 327-333.
ABUH, M.A., ABIA-BASSEY, N., UDEINYA, T.C., NWANNEWUIHE, H.U., ABONG, A.A., AKPOMIE, K.G.,
2014. Industrial Potentials of Adiabo Clay in Calabar Municipal of Cross River State South-South Nigeria. Asia Pac. J.
Sci. Technol. 15, 1, 63-75.
AJEMBA, R.O., ONUKWULI, O.D., 2012. Kinetic Model for Ukpor Clay Dissolution in Hydrochloric Acid Solution.
J. Emer. Trends Eng. Appl. Sci. 3, 448–454.
ANTONIJEVIC, M.M., JANKOVIC, Z.D., DIMITRIJEVIC, M.D., 2004. Kinetics of Chalcopyrite Dissolution by Hydrogen
Peroxide in Sulphuric Acid. Hydrometallurgy. 71, 3, 329-334.
AMBIKADEVI, V.R., LALITHAMBIKA, M., 2000. Effect of Organic Acids on Ferric Iron Removal from Iron-
Stained Kaolinite. Appl. Clay Sci. 16, 133-145.
AYANDA, O.S., ADEKOLA, F.A., 2012. Leaching of Nigerian Columbite in Hydrochloric Acid: Dissolution Kinetics. Int.
J. Metall. Eng. 1, 3, 35-39.
BABA, A.A., ADEKOLA, F.A., 2012. A Study of the Dissolution Kinetics of a Nigerian Galena Ore in Hydrochloric
Acid. J. Saudi Chem. Soc. 16, 4, 377-386.
BABA, A.A., ADEKOLA, F.A., BALE, R.B., 2009. Development of a Combined Pyro- and Hydrometallurgical Route to
Treat Zinc-Carbon Batteries. J. Hazard. Mater. 171, 1, 838-844.
BABA, A.A., MOSOBALAJE, M.A., IBRAHIM, A.S., GIRIGISU, S., ELETTA, A.A., ALUKO, F.I., ADEKOLA, F.A.,
109 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

2015. Bleaching of Nigerian Kaolin by Oxalic Acid Leaching. J. Chem. Technol. Metall. 50, 5, 623-630.
BABA, A.A., OLUMODEJI, O.O., ADEKOLA, F.A., LAWAL, M., AREMU, A.S., 2014. Quantitative Leaching of a Spent
Cell Phone Printed Circuit Board by Hydrochloric Acid. Metall. Mater. Eng. 20, 2, 119-129.
BONNEVILLE, S., BEHRENDS, T., VANCAPPELLEN, P., 2009. Solubility and Dissimilatory Reduction Kinetics of
Iron(III) Oxyhydroxides: A Linear Free Energy Relationship. Geochim. Cosmochim. Ac. 73, 5273-5282.
CELIK, A.G., KILIC, A.M., CAKAL, G.O., 2013. Expanded Perlite Aggregate Characterization for use as a Lightweight
Construction Raw Material. Physicochem. Probl. Miner. Process. 49, 2, 689-700.
CELIK, H., 2010. Technological Characterization and Industrial Application of Two Turkish Clays for the Ceramic Industry.
Appl. Clay Sci. 50, 245-254.
CETINTAS, S., BINGOL, D., 2020. Dissolution Kinetics of Manganese during Nickel Recovery from High Iron Grade
Laterite by Acid Leaching Combined Naoh-Assisted Mechanochemical Technology. Cumhuriyet Sci. J. 41,2, 397-406.
CHANG, L.L.Y., 2002. Industrial Mineralogy Materials, Processes and Uses. New Jersey: Prentice Hall, USA.
CORNELL, R.M., SCHWERTMANN, U., 2003. The Iron Oxides: Structure, Properties, Reactions, Occurrence and Uses,
Wiley-VCH Publishers, New York, USA.
DEHGHAN, R., NOAPARAST, M., KOLAHDOOZAN, M., 2009. Leaching and Kinetic Modelling of Low-Grade
Calcareous Sphalerite in Acidic Ferric Chloride Solution. Hydrometallurgy. 96, 4, 275-282.
DU, R.L., WU, K., XU, D.A., CHAO, C.Y., ZHANG, L., DU, X.D., 2016. A Modified Arrhenius Equation to Predict the
Reaction Rate Constant of Anyuan Pulverized-Coal Pyrolysis at Different Heating Rates. Fuel Process. Technol. 148,
295-301.
ERDOGAN, Y., 2015. Physicochemical Properties of Handere Clays and Their use as a Building Material. J. Chem. 1, 1-
6.
FABIO, L.M., FABIO, L., SUSANA, M.S., MONICA, R., PAULO, S.P., CARLOS, R.A., 2009. Chemical
Characterization of Clay SRM by X-Ray Fluorescence Results Comparison from Different Laboratories. Semina: Cienc.
Exatas Tecnol. 30, 2, 145-150.
FADIL-DJENABOUA, S., NDJIGUIA, P.D., MBEY, J.A., 20 15 . Mineralogical and Physicochemical Characterization of
Ngaye Alluvial Clays (Northern Cameroon) and Assessment of Its Suitability in Ceramic Production. J. Asian Ceram.
Soc. 3, 50-58.
GAO, L., RAO, B., DAI, H., XIE, H., WANG, P., MA, F., 2019. Kinetics of Sulphuric Acid Leaching of Titanium from
Refractory Anatase under Atmospheric Pressure. Physicochem. Probl. Miner. Process. 55, 2, 467-478.
GARG, N., SKIBSTED, J., 2019. Dissolution Kinetics of Calcined Kaolinite and Montmorillonite in Alkaline Conditions:
Evidence for Reactive Al(V) Sites. J. Am. Ceram. Soc. 102, 12, 7720-7734.
GATES, W.P., ANDERSON, J.S., RAVEN, M.D., CHURCHMAN, G.J., 2002. Mineralogy of a Bentonite from Miles,
Queensland, Australia and Characterization of Its Acid Activation Products. Appl. Clay Sci. 20, 4, 189-197.
GBOR, P.K., JIA, C.Q., 2004. Critical Evaluation of Coupling Particle Size Distribution with the Shrinking Core Model.
Chem. Eng. Sci. 59, 1979-1987.
GHASSA, S., NOAPARAST, M., SHAFAEI, S.Z., ABDOLLAHI, H., GHARABAGHI, M., BORUOMAND, Z., 2017.
A Study on the Zinc Sulfide Dissolution Kinetics with Biological and Chemical Ferric Reagents. Hydrometallurgy, 171,
362-373.
HERNANDEZ, R.A., GARCIA, F.L., HERNANDEZ, L.E., LUEVANOS, A.M., 2013. Iron Removal from Kaolinite Clay
by Leaching to Obtain Whiteness Index. 3rd Congress on Materials Science and Engineering. 1-5.
HOIDY, W.H., AHMAD, B.A., MULLER, J.A., IBRAHIM, N.A., 2009. Synthesis and Characterization of Organoclay
from Sodium Montmorillonite and Fatty Hydroxamic Acids. Am. J. Appl. Sci. 6, 8, 1567-1572.
HURSIT, M., LACIN, O., SARAC, H., 2009. Dissolution Kinetics of Smithsonite Ore as an Alternative Zinc Source with
an Organic Leach Reagent. J. Taiwan Inst. Chem. Eng. 40, 6-12.
LEGORRETA, F., SALINAS, E., CERECEDO, E., 2015. Kinetics Study of Iron Leaching from Kaolinitic Clay Using Oxalic
Acid. Eur. Sci. J. 11, 12, 12-23.
LEE, O.S., TAM, T., YI, Y.P., SEONG, J.K., MYONG, J.K., 2006. Study on the Kinetics of Iron Oxide Leaching by
Oxalic Acid. Int. J. Miner. Process. 80, 2, 144-152.
LI, J., XU, Z., WANG, R., GAO, Y., YANG, Y., 2019. Study on Leaching Kinetics of Laterite Ore Using Hydrochloric Acid.
Physicochem. Probl. Miner. Process. 55, 3, 711-720.
110 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

LI, M., ZHENG, S., LIU, B., DU, H., DREISINGER, D.B., TAFAGHODI, L., ZHANG, Y., 2017. The Leaching Kinetics
of Cadmium from Hazardous Cu-Cd Zinc Plant Residues. Waste Manage. 65, 128-138.
LIMA, P.E.A., ANGÉLICA, R.S., NEVES, R.F., 2017. Dissolution Kinetics of Amazonian Metakaolin in Hydrochloric Acid.
Clay Miner. 52, 75–82.
LORI, J.A., LAWAL, A.O., EKANEM, E.J., 2007. Characterization and Optimization of Deferration of Kankara Clay. J.
Eng. Appl. Sci. 2, 5, 60-74.
MACCARTHY, J., NOSRATI, A., SKINNER, W., ADDAIMENSAH, J., 2016. Atmospheric Acid Leaching Mechanisms
and Kinetics and Rheological Studies of a Low Grade Saprolitic Nickel Laterite Ore. Hydrometallurgy. 160, 26-37.
MADEJOVA, J., BUJDAK, J., JANEK, M., KOMADEL, P., 1998. Comparative FT-IR Study of Structural Modifications
during Acid Treatment of Dioctahedral Smectites and Hectorite. Spectrochim. Acta, Part A. 54, 1397-1406.
MANDAL, S.K., BANERJEE, P.C., 2 0 0 4 . Iron Leaching from China Clay with Oxalic Acid: Effect of Different
Physico-Chemical Parameters. Int. J. Miner. Process. 74, 263-270.
MILOŠEVIĆ, M., LOGAR, M., KALUĐEROVIĆ, L., JELIĆ, I., 2017. Characterization of Clays from Slatina (Serbia)
for Potential Uses in the Ceramic Industry. Energy Procedia. 125, 650-655.
MURRAY, H.H., 1999. Applied Clay Mineralogy Today and Tomorrow. Clay Miner. 34, 39-49.
NAVIAUX, J.D., SUBHAS, A.V., ROLLINS, N.E., DONG, S., BERELSON, W.M., ADKINS, J.F., 2019. Temperature
Dependence of Calcite Dissolution Kinetics in Seawater. Geochim. Cosmochim. Acta. 246, 363-384.
NJOKA, E.N., OMBAKA, O., GICHUMBI, J.M., KIBAARA, D.I., NDERI, O.M., 2015. Characterization of Clays from
Tharaka-Nithi County in Kenya for Industrial and Agricultural Applications. Afr. J. Environ. Sci. Technol. 9, 3, 228-
243.
NZEUKOU, A.N., FAGEL, N., NJOYA, A., KAMGANG, M.V., MEDJO, R.E., MELO, U.C., 2013. Mineralogy and
Physicochemical Properties of Alluvial Clays from Sanaga Valley (Center, Cameroon): Suitability for Ceramic
A pplication. Appl. Clay Sci. 83, 238-243.
RAHMAN, M.A., MUNEER, M., 2005. Photocatalysed Degradation of Two Selected Pesticide Derivatives, Dichlorvos and
Phosphamidon in Aqueous Suspensions of Titanium Dioxide. Desalination. 181, 1, 161-172.
PANIAS, D., TAXIARCHOU, M., DOUNI, I., PASPALIARIS, I., KONTOPOULOS, A., 1996. Thermodynamic Analysis
of the Reactions of Iron Oxides: Dissolution in Oxalic Acid. Can. Metall. Q. 35, 363-373.
PARIYAN, K., HOSSEINI, M.R., AHMADI, A., ZAHIRI, A., 2019. Optimization and Kinetics of Oxalic Acid Treatment
of Feldspar for Removing the Iron Oxide Impurities. Sep. Sci. Technol. 55, 2, 1-12.
SAIKIA, N.J., BHARALI, D.J., SENGUPTA, P., BORDOLOI, D., GOSWAMEE, R.L., SAIKIA, P.C., BORTHAKUR,
P.C., 2003. Characterization, Beneficiation and Utilization of a Kaolinite Clay from Assam, India. Appl. Clay Sci. 24, 93-
103.
SAKLAR, S., YORUKOGLU, A., 2015. Effects of Acid Leaching on Halloysite. Physicochem. Probl. Miner. Process. 51,
1, 83-94.
SANDA, O., TAIWO, E.A., 2016. Investigation of Dissolution Kinetics of a Nigerian Columbite in Hydrofluoric Acid Using
the Shrinking Core Model. Niger. J. Technol. 35, 4, 841-846.
SANDLER, A., 2013. Clay Distribution over the Landscape of Israel: from the Hyper-Arid to the Mediterranean Climate
Regimes. Catena. 110, 119-132.
SANTOS, M.F.M., FUJIWARA, E., SCHENKEL, E.A., ENZWEILER, J., SUZUKI, C.K., 2015. Processing of Quartz
Lumps Rejected by Silicon Industry to Obtain a Raw Material for Silica Glass. Int. J. Miner. Process. 135, 65-70.
SEYED-GHASEMI, S.M., AZIZI, A., 2017. Investigation of Leaching Kinetics of Zinc from a Low-Grade Ore in Organic
and Inorganic Acids. J. Min. Environ. 8, 4, 579-591.
SHI, Z., BONNEVILLE, S., KROM, M.D., CARSLAW, K.S., JICKELLS, T.D., BAKER, A.R., BENNING, L.G., 2011.
Iron Dissolution Kinetics of Mineral Dust at Low pH During Simulated Atmospheric Processing. Atmos. Chem. Phys.
11, 995-1007.
SULTANA, U.K. GULSHAN, F., KURNY, A.S.W., 2014. Kinetics of Leaching of Iron Oxide in Clay in Oxalic Acid and
in Hydrochloric Acid Solutions. Mater. Sci. Metall. Eng. 2, 1, 5-10.
SULTANA, U.K., KURNY, A.S.W., 2012. Dissolution Kinetics of Iron Oxides in Clay in Oxalic Acid Solutions. Int. J.
Miner. Metall. Mater. 19, 1083-1087.
TANDA, B.C., EKSTEEN, J.J., ORABY, E.A., 2018. Kinetics of Chalcocite Leaching in Oxygenated Alkaline Glycine
Solutions. Hydrometallurgy. 178, 264-273.
TAO, L., WANG, L., YANG, K., WANG, X., CHEN, L., NING, P., 2021. Leaching of Iron from Copper Tailings by
Sulfuric Acid: Behavior, Kinetics and Mechanism. RSC Adv. 11, 5741-5752.
111 Physicochem. Probl. Miner. Process., 57(3), 2021, 97-111

TEMUUJIN, J., JADAMBAA, T., BURMAA, G., ERDENECHIMEG, S., AMARSANAA, J., MACKENZIE, K.J.,
2004. Characterization of Acid Activated Montmorillonite Clay from Tuulant (Mongolia). Ceram. Int. 30, 251-255.
TEMUUJIN, J., OKADA, K., JADAMBAA, T., MACKENZIE, K.J.D., AMARSANAA, J., 2002. Effect of Grinding
on the Preparation of Porous Material from Talc by Selective Leaching. J. Mater. Sci. Lett. 21, 1607-1609.
TUNCUK, A., AKCIL, A., 2016. Iron Removal in Production of Purified Quartz by Hydrometallurgical Process. Int.
J. Miner. Process. 153, 1-29.
VAPUR, H., TOP, S., DEMIRCI, S., 2017. Purification of Feldspar from Colored Impurities Using Organic Acids.
Physicochem. Probl. Miner. Process. 53: 150-160.
VITRA, R.L., 2009. U.S. Geological Survey, Mineral Commodity Summaries: Clays. Washington: United States
Government Printing Office, USA.
WU, M.C., KUO, S.L., LIN, J.C., MA, C.M., HONG, G.B., CHANG, C.T., 2011. Studies on Certain Physical Properties
of Modified Smectite Nanocatalysts. Appl. Surf. Sci. 257, 13, 5641-5646.
YANG, C.Q., LI, S.Q., 2020. Kinetics of Iron Removal from Quartz under Ultrasound-Assisted Leaching. High Temp.
Mater. Process. 39, 1, 395-404.
ZHANG, C., MIN, X.B., ZHANG, J.Q., WANG, M., LI, Y.C., FEI, J.C., 2016. Reductive Clean Leaching Process of
Cadmium from Hydrometallurgical Zinc Neutral Leaching Residue Using Sulfur Dioxide. J. Clean Prod. 113, 1, 910-
918.
ZHANG, Q., WEN, S.M., FENG, Q.C., NIE, W.L., WU, D.D., 2017. Dissolution Kinetics of Hemimorphite in Methane
Sulfonic Acid. Physicochem. Probl. Miner. Process. 55, 1, 1-9.
ZHANG, Q., WEN, S.M., WU, D.D., FENG, Q.C., LI, S., 2019. Dissolution Kinetics of Hemimorphite in Trichloroacetic
Acid Solutions. J. Mater. Res. Technol. 8, 2, 1645-1652.
ZHONG, L., LEI, S., WANG, E., PEI, Z., LI, L., YANG, Y., 2013. Research on Removal Impurities from Vein Quartz Sand
with Complexing Agents. Appl. Mech. Mater. 454, 194-199.